Treatment and after-treatment of metal with polyphenol compounds

ABSTRACT

A metal treatment solution comprising an effective amount of a soluble or dispersible compound which is a derivative of a polyphenol. A composition for treatment and after treatment of metal with polyphenol compounds is provided. The present invention includes novel derivatives of polyphenol compounds which are useful in surface treatment solutions or dispersions. A method for using these solutions or dispersions is also provided. The molecular weight of the polyphenols used to form the derivatives of the present invention are in the range of from about 360 to 30,000 or greater. The resulting derivatives of the present invention typically have a molecular weight of up to about 2,000,000 with molecular weights within the range of about 700 to about 70,000 being preferred.

BACKGROUND AND SUMMARY OF INVENTION

The present invention relates to the field of protective and/ordecorative surface treatment of articles, particularly metals, plastics,and the like.

The present invention comprises novel derivatives of polyphenolcompounds useful in the treatment of the surface of metal articles. Thepresent invention also encompasses novel surface treatment solutions ordispersions, and methods of using these solutions or dispersions.

In accordance with the present invention, novel compositions, solutionsand dispersions, and methods are provided for use in providing aprotective or decorative metal surface treatment; these include thetreatment of previously untreated bare metal surfaces, thepost-treatment of phosphatized or conversion coated metal surfaces, theapplication of a paint or other decorative coating or film, and thelike. The present invention additionally includes compositions andmethods that are particularly useful for treating various metal surfacesincluding aluminum, steel and zinc metal surfaces. The compositions,solutions and dispersions, and methods of the present invention providea coating on the metal surface which is effective in enhancing thecorrosion resistance and paint adhesion characteristics of the metalsurface whether previously conversion coated or not. A further and moredetailed understanding of this invention can be obtained from thefollowing disclosure. All parts and percentages are by weight unlessotherwise indicated.

The need for applying protective coatings to metal surfaces for improvedcorrosion resistance and paint adhesion characteristics is well known inthe metal finishing art as well as in other metal arts. Traditionally,metal surfaces are treated with chemicals which form a metal phosphateand/or metal oxide conversion coating on the metal surface to improvethe corrosion resistance and paint adhesion thereof. The conversioncoated metal surfaces are also generally rinsed or post-treated with asolution containing a hexavalent chromium compound for even greatercorrosion resistance and paint adhesion.

Because of the toxic nature of hexavalent chromium, expensive wastewatertreatment equipment must be employed to remove the residual chromatesfrom plant effluent to comply with environmental regulations and toimprove the quality of rivers, streams, and drinking water sources.Hence, although the corrosion resistance and paint adhesioncharacteristics of conversion coated metal surfaces can be enhanced byan after-treatment solution containing hexavalent chromium, thesedisadvantages in recent years have lead to much research and developmentin an effort to uncover effective alternatives to the use ofpost-treatment solutions containing hexavalent chromium. One alternativeto the use of hexavalent chromium involves the use of derivatives ofpolyphenol compounds such as poly-vinyl phenol. Suitable derivatives andsuitable treatment solutions are disclosed in earlier U.S. Pat. Nos.4,517,028, May 14, 1985; 4,376,000, Mar. 8, 1983 to Lindert; and4,433,015, Feb. 21, 1984 to Lindert and 4,457,790, July 3, 1984 toLindert, et al.; all of which are expressly incorporated herein byreference. Also see the two commonly assigned applications filed thesame date herewith entitled "Treatment And After-Treatment Of Metal WithCarbohydrate-Modified Polyphenol Compounds", U.S. Ser. No. 128,673, nowU.S. Pat. No. 4,963,596; and "Treatment and After-Treatment Of MetalWith Amine Oxide-Containing Polyphenol Compounds", U.S. Ser. No. 128,756now U.S. Pat. No. 4,970,264; both of which are expressly incorporatedherein by reference.

DETAILED DESCRIPTION OF THE INVENTION

In a typical protective metal surface treatment operation employing thisinvention, the metal to be treated is initially cleaned by a chemical orphysical process and then water rinsed to remove grease and dirt fromthe surface. The metal surface is then brought into contact with thetreatment solution of this invention. Alternatively, and preferably,instead of contacting the metal surface with the treatment solution ofthis invention immediately following the cleaning process, a conversioncoating solution is applied to or otherwise used to pre-treat the metalsurface in a conventional manner to form a conversion coating thereon.Then the conversion coated surface is water rinsed and the metal surfaceis brought into contact with the treatment solutions of the presentinvention.

Although solutions and/or dispersions of the invention can beeffectively applied to treated or untreated metal surfaces, speakinggenerally the present invention is particularly useful if the metalsurface has previously been conversion coated and the invention isaccordingly used as a post-treatment; accordingly, as used herein, theterm "post-treatment" means the treatment of a metal surface which isnot bare metal, and preferably has been previously treated with aconventional conversion coating process. Such conversion coatings arewell known and have been described, for example, in Metal Handbook,Volume II, 8th Edition, pp. 529-547 of the American Society for Metalsand in Metal Finishing Guidebook and Directory, pp. 590-603 (1972), thecontents of both of which are specifically incorporated by referenceherein.

The compositions and processes of the present invention are useful intreating a broad range of metal surfaces, including metals havingsurfaces that have been conversion coated with suitable conversioncoatings such as iron phosphate, manganese phosphate, zinc phosphate,zinc phosphate modified with calcium, nickel, or manganese ions.Examples of suitable metal surfaces include zinc, iron, aluminum andcold-rolled, polished, pickled, and hot-rolled steel and galvanizedsteel surfaces. As used herein, the term "metal surface" includes bothuntreated metal surfaces and conversion coated metal surfaces.

The polyphenol compounds of the present inventions are Polymer MaterialsI, II and III, their salts, and mixtures thereof. The treatmentcompositions of the present invention comprise an effective amount of asoluble or dispersible treatment compound (Polymer Material) in acarrier that is suitable for surface treatment, i.e., one that allowsthe selected Polymer Material to be deposited or otherwise placed on thesurface of, for example, a metal. The soluble or dispersible compoundemployed in the present invention is selected from the group consistingof any one of the following Polymer Materials I, II or III(characterized below), solutions or dispersions of these PolymerMaterials, their salts, and mixtures thereof. Salts include the acid andalkaline salts thereof.

The methods of the present invention comprise contacting a metal surfacewith treatment compositions described herein.

Polymer Materials I, II, and III are as follows.

POLYMER MATERIAL I

Polymer Material I comprises a material, preferably a homo- orco-polymer compound, having at least one repeating unit having theformula: ##STR1## where:

R₁, R₂, R₁₃ and R₁₄ are independently selected for each repeating unitfrom hydrogen, an alkyl group having from 1 to about 5 carbon atoms, oran aryl group having about 6 to about 18 carbon atoms;

Y₂ is independently selected for each repeating unit from hydrogen, Z,--CR₁₁ R₅ OR₆, --CH₂ Cl, or an alkyl or aryl group having from 1 toabout 18 carbon atoms; preferably at least a fraction of one Y₂ is Z;##STR2##

R₅ through R₁₂ are independently selected for each repeating unit fromhydrogen, alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl, orphospho-alkyl moiety. Preferably, R₁ or R₇ through R₁₂ are, in total,carbon chain lengths up to that at which the compound is no longersoluble or dispersible in a suitable surface treatment carrier, such aswater. R₁₂ can also be --O.sup.(-1) or --OH (oxygen or hydroxy) in orderto form an amine oxide or a hydroxyl amine.

W₂ is independently selected for each repeating unit from the groupconsisting of hydrogen; acyl; acetyl; benzoyl;3-allyloxy-2-hydroxy-propyl-; 3-benzyloxy-2-hydroxy-propyl-;3-alkylbenzyloxy-2-hydroxy-propyl-; 3-phenoxy-2-hydroxy-propyl-;3-alkylphenoxy-2-hydroxy-propyl-; 3-butoxy-2-hydroxy-propyl;3-alkyloxy-2-hydroxy-propyl; 2-hydroxyoctyl-; 2-hydroxy-alkyl-;2-hydroxy-2-phenyl ethyl-; 2-hydroxy-2-alkyl phenyl ethyl- isopropenyl-propenyl-; benzyl-; methyl-; ethyl-; propyl-; alkyl; allyl; alkylbenzyl-; haloalkyl-; haloalkenyl; 2-chloro-propenyl-; sodium, potassium;tetra aryl ammonium; tetra alkyl ammonium; tetra alkyl phosphonium;tetra aryl phosphonium; or a condensation product of ethylene oxide,propylene oxide, or a mixture or copolymer thereof.

It will be appreciated that the depiction above represents a repeatingunit that characterizes the compound or materials of the presentinvention; no terminating end units are depicted. The end group notdepicted of the polymers of the present invention can be selected by theskilled artisan relying upon art-disclosed techniques. For example, theend groups of the polymer may either be those resulting from thespecific polymerization process employed or those intentionally added toalter the polymer characteristics. For example, the end groups may behydrogen, hydroxyl, initiation fragments, chain transfer agents,disproportionation groups, or other similar methods of terminating agrowing polymer chain.

POLYMER MATERIAL II

Polymer Material II comprises copolymers of alkenylphenols andsubstituted alkenylphenols co-polymerized with one or more monomers.Preferably the monomers possess an ethylenically unsaturated C═C bond.The alkenylphenolic or substituted alkenylphenolic moieties of theco-polymer compositions have the following structure: ##STR3##

R₁ through R₃ are independently selected for each repeating unit fromhydrogen, an alkyl group having from 1 to about 5 carbon atoms or anaryl group having from about 6 to about 18 carbon atoms;

Y₁ through Y₄ are independently selected for each repeating unit fromhydrogen, Z, --CR₄ R₅ OR₆, --CH₂ Cl, or an alkyl or aryl group havingfrom 1 to 18 carbon atoms; preferably at least a fraction of one of theY₁ through Y₄ units is Z.

Z is ##STR4##

R₄ through R₁₂ are independently selected for each repeating unit fromhydrogen, an alkyl, aryl, hydroxy-alkyl amino-alky, mercapto-alkyl orphospho-alkyl moiety. Preferably, R₁ or R₄ through R₁₂ are carbon chainlengths up to a length at which the compound is no longer soluble ordispersible in a suitable surface treatment carrier, such as water. R₁₂can also be --O.sup.(-1) or --OH in order to form an amine oxide orhydroxyl amine.

W₁ is independently selected for each repeating unit from the groupconsisting of a hydrogen; an acyl moiety; acetyl; benzoyl;3-allyloxy-2-hydroxy-propyl-; 3-benzyloxy-2-hydroxy-propyl-;3-alkylbenzyloxy-2-hydroxy-propyl-; 3-phenoxy-2-hydroxy-propyl-;3-alkylphenoxy-2-hydroxy-propyl-; 3-butoxy-2-hydroxy-propyl-;3-alkyloxy-2-hydroxy-propyl-; 2-hydroxyoctyl-; 2-hydroxy-alkyl-;2-hydroxy-2-phenyl-ethyl-; 2-hydroxy-2-alkylphenylethyl-; benzyl-;methyl-; ethyl-; propyl-; alkyl; allyl-; alkylbenzyl-; haloalkyl-; orhaloalkenyl such as 2-chloro-propenyl-; or a condensation product ofethylene oxide, propylene oxide, or a mixture or copolymer thereof.

Materials having C═C moieties and useful copolymerizable monomercomponents for use in the present invention can be selected from avariety of unsaturated materials as depicted in the following list. Thematerial may be selected from the group consisting of acrylonitrile,methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate,vinyl methyl ketone, isopropenyl methyl ketone, acrylic acid,methacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate,styrene, m-chlorostyrene, o-chlorostyrene, p-chlorostyrene, n-decylmethacrylate, N,N-diallylmelamine, N,N-di-n-butylacrylamide, di-n-butylitaconate, di-n-butyl maleate, diethylaminoethyl 3methacrylate,diethyleneglycol monovinyl ether, diethyl fumarate, diethyl itaconate,diethyl vinylphosphonate, vinylphosphonic acid, diisobutyl maleate,diisopropyl itaconate, diisopropyl maleate, dimethyl fumarate, dimethylitaconate, dimethyl maleate, di-n-nonyl fumarate, di-n-nonyl maleate,dioctyl fumarate, di-n-octyl itaconate, di-n-propyl itaconate, n-dodecylvinyl ether, ethyl acid fumarate, ethyl acid maleate, ethyl acrylate,ethyl cinnamate, N-ethylmethacrylamide, ethyl methacrylate, ethyl vinylether, 5-ethyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine 1-oxide,glycidyl acrylate, glycidyl methacrylate, n-hexyl methacrylate,2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobutylmethacrylate, isobutyl vinyl ether, isoprene, isopropyl methacrylate,isopropyl vinyl ether, itaconic acid, lauryl methacrylate,methacrylamide, methacrylic acid, methacrylonitrile,N-methylolacrylamide, N-methylolamethacrylamide,N-alkoxymethylacrylamide, N-alkoxymethylmethacrylamide,N-butoxymethylmethacrylamide, N-vinyl-caprolactam, methyl acrylate,N-methylmethacrylamide,

αmethylstyrene, m-methylstyrene, o-methylstirene, p-methylstyrene,2-methyl-5-vinylpyridine, n-propyl methacrylate, sodiump-styrenesulfonate, stearyl methacrylate, styrene, p-styrenesulfonicacid, p-styrenesulfonamide, vinyl bromide, 9-vinylcarbazole, vinylchloride, vinylidene chloride, 1-vinylnaphthalene, 2-vinylnaphthalene,2-vinylpyridine, 4-vinylpyridine, 2-vinylpyridine N-oxide,4-vinylpyrimidine, and N-vinylpyrrolidone. Mixtures of these materialsmay also be employed.

It is appreciated by those skilled in the art that the alkenylphenolicmoieties of the present invention can be either randomly distributedwithin the co-polymer and terpolymer or can be synthesized to constitutea block orientated polymer, depending upon the methods and conditionsused for polymerization.

Preferred final materials are based on a vinyl phenolic moiety orαmethyl vinyl phenolic moiety. For example, a vinyl phenol orisopropenylphenol and derivatives thereof may be used.

POLYMER MATERIAL III--CONDENSATE POLYMERS

By the term "condensation polymers" is meant the following:

A condensation polymer is a material wherein condensable forms (modifiedto be condensable as noted below) of Polymer Material I, II, or mixturesthereof, are condensed with a second compound selected from the groupconsisting of phenols (preferably phenol, alkyl phenol, aryl phenol,cresol, resorcinol catechol, pyrogallol) tannins (both hydrolyzable orcondensed), novolak resins, lignin compounds, and mixtures thereof,together with an aldehyde, ketone, or mixture thereof, to produce acondensation resin prepolymer product that is a prepolymer of PolymerMaterial III. The condensable or modified starting materials aremodified by initially failing to include the "Z" moiety prior toinitiating condensation; an additional modification to make the startingmaterials condensable will also be appreciated as necessary in that Y₁through Y₄ cannot be Z, --CR₁₁ R₅ OR₆, or --CR₄ R₅ OR₆. The "Z" moiety(as described above) is then added later to these condensationprepolymers by again reacting the condensation resin with (1) analdehyde, ketone, or mixtures thereof, and (2) a secondary amine toproduce an adduct which can react with acid and/or can be reacted withhydrogen peroxide to generate an amine oxide and can be used in water orin an organic solvent. If desired the amine oxide can be acidneturalized to form the hydroxylamine.

While this condensation product is described for convenience as beingprepared by a sequential reaction, it will be appreciated that thesematerials can be prepared by carrying out the necessary steps in anyorder, or simultaneously. However, the sequence described is preferred.

The surface treatment solutions of this invention comprise PolymerMaterials I, II, III, or mixtures thereof (with or without therequirement that the Z moiety be present), are preferably dissolved ordispersed in a carrier suitable for depositing or otherwise placing thePolymer Material on the surface of a metal, i.e., as a metal surfacetreatment, metal surface post treatment, a paint, protective film, or asa component of any of the foregoing.

These Polymer Materials of the present invention may be made soluble ordispersible in water or organic solvent-type carriers. They maytherefore be employed as a treatment solution when dissolved in water orin an organic solvent such as, for example, ethanol. Preferably,however, the Polymer Material selected is used in aqueous solution as acarrier.

Accordingly, it is highly desirable to provide or improve the watersolubility or water dispersibility of the selected Polymer Material.This is preferably done with an acid used for neutralization and/orcomplexation of a "Z" moiety thereof (if present). Such acids may beorganic or inorganic. Useful and preferred acids for this purposeinclude carbonic acid, acetic acid, citric acid, oxalic acid, ascorbicacid, phenylphosphonic acid, chloromethylphosphonic acid; mono, di andtrichloroacetic acid, trifluoroacetic acid, nitric acid, phosphoricacid, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid,hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid,and the like; these may be employed alone or in combination with eachother and may be neutralized by conventional acid-base reactions or bycomplexing. In a highly preferred embodiment, the addition of water tothe neutralized, overneutralized or partially neutralized treatmentcompounds mentioned above results in a water soluble or dispersiblesolution or emulsion of the polymer useful for metal treatment.

Alternately, the final Polymer Material/polyphenol compounds of thepresent invention can be made water soluble or dispersible byneutralization of the phenolic group with an organic or inorganic base.Suitable bases for this purpose include tetra-alkylammonium hydroxidessuch as tetrabutylammonium hydroxide, tetra arylammonium hydroxide,sodium hydroxide, potassium hydroxide and the like.

In a highly preferred embodiment, the final Polymer Material can beprepared such that the "Z" moiety does not require neutralization, i.e.,an amine oxide or the like.

Within such materials, the ratio of any single monomer to any othermonomer can be about 1:99 to about 99:1, preferably about 5:1 to about1:5, and more preferably 1.5:1 to about 1:1.5.

The molecular weight of the polyphenols used in the preparation ofderivatives claimed in the present invention can be a dimer, but maypreferably be low molecular weight oligomers or resinous polymers havingmolecular weights in the range of about 360 to about 30,000 or greater.The upper limit molecular weight of materials useful in surfacetreatment compositions is generally determined by the functionallimitation that the derivative therefrom must be soluble or dispersiblein the selected carrier. The resulting derivatives of the formulae setforth hereinabove will typically have a molecular weight of up to about2,000,000 with molecular weights within the range of about 700 to about70,000 being preferred.

Typically, the pH of the aqueous solution will vary from about 0.5 toabout 14. Generally the aqueous solution will have a pH of from about2.0 to about 12 both for the stability of the solution and for bestresults on the treated metal surfaces.

It is contemplated that the compositions and treatment solutions of thepresent invention can be used to treat the surface of a variety ofmaterials, particularly metal and plastic or "plastic-like" surfaces.Preferred metal surfaces include iron-, zinc- and aluminum-based metals.Preferred "plastic-like" material surfaces include resin or polymericmaterials, including thermoplastic and thermosetting materials, as wellas natural rubbers, mixtures of these materials and the like.

The coating applied may be for protection or decorative in nature, ormay be a preparation of the surface for another treatment; it may alsoserve several functions at once.

The thickness of the final dry or cured coating will depend on itspurposes or functions, and may typically range from about 0.0001 mil toabout 25 mil or greater. The typical and preferred metal surfacetreatment (such as a conversion-type protective/paint base coating) isin the range of about 0.05 mil and below, and more preferably about0.0001 mil to about 0.05 mil. When acting as a paint or decorative andprotective surface treatment, the resulting coating thickness is about0.05 mil and above, preferably about 0.05 to about 25 mils, and morepreferably about 0.05 to about 10 mil.

It is further contemplated that the treatment compounds of the presentinvention will generally be used in surface treatment compositions overa wide range of concentrations. It will be appreciated that the levelsof use or useful ranges will vary with many factors well-known to theskilled artisan. Useful levels of the compositions of the presentinvention dissolved or dispersed in a carrier may be in the range ofabout 0.001% to about 80 percent, depending upon the ultimate use. Forexample, when used as a pre- or post-treatment of a metal surface,useful levels typically include a dilute to moderate concentration offrom about 0.001% to about 20%, by weight, preferably about 0.001% toabout 10 percent, by weight, and still more preferably about 0.001% toabout 5% by weight. Practically speaking, a concentration of 0.0025 to1% is preferred in metal surface treatment compositions (especially foriron-, zinc-, or aluminum-based metal surfaces). However, under somecircumstances (for example when transporting or storing the solution orwhen using it in a "dry-in-place" system), a concentrate of the solutionmay be preferred. Higher levels (for example, as high as 80% by weight)may also be employed when the treatment composition is part of a paintsystem.

Of course, the treatment solutions of the present invention can alsocomprise ingredients typically found in other similar treatmentcompositions, (e.g., conversion coating compositions) in addition to thepolymer compound. For example, the treatment solution may optionallycomprise an effective amount of a treatment compound according to thepresent invention, and from about 0.001% to about 3.0% of a metal ion.Metal ions useful for metal treatment in combination with polyphenols ofthis invention include first row transition metals generally, GroupIV-B-metals generally, iron, nickel, cobalt, vanadium, chromium,titanium, zirconium hafnium, scandium, yttrium, lanthanum and theirrespective Lanthanoid and Actinoid metals, as well as molybdenum andtungsten. In addition, tin, silicon, and aluminum compounds, and inparticular their oxides, in combination with the materials of thepresent invention can be used to improve both the effectiveness orperformance of the treatment solution in use. Such materials may alsoreduce the time of application of treatment solution to the metalsurface to as short a time as about 2 to 5 seconds as might be requiredon a coil coating line. Complex fluoride materials may also be employed.For example, suitable complex fluoride materials include: BF₄.sup.(-1),NH₄ HF₂, hexafluoride and the like.

It must be appreciated that the addition of metal ions may result in theformation of polymer-metal ion chelating compounds.

The Polymer Materials of the present invention may also be employed insurface treatment compositions and surface treatment methods other thanthose described above. For example, the Polymer Material of the presentinvention may be employed as a component of a dry-in-place system, apaint system, or as an additive in a system needing a crosslinkingagent.

For example, the Polymer Materials of the present invention may be usedin a film forming composition that includes a pigment, i.e. may be usedas a paint. They may also be employed as an additional component inconjunction with other polymeric materials in a paint system. ThePolymer Materials of the present invention are particularly useful incathodic electrocoat surface treatment compositions. Such protective,functional and/or decorative surface treatment solutions preferablyemploy typical electrocoat/electrodeposition additives at theirart-established levels. The polymer materials of the present inventionmay be employed as a solubilizing polymer and/or binder in anelectro-coat paint. They may be so employed alone or in conjunction withother binder resins. For example, such paint compositions may optionallyinclude pigments (both organic and inorganic); film forming resins,binders such as epoxies, oils, alkyds, acrylics, vinyls, urethanes,phenolics, etc.; and solvents including hydrocarbons, chlorinatedaliphatics and aromatics, alcohols, ethers, ketones, esters; nitratedmaterials; and particulate zinc.

Further, the Mannich derivatives of the present invention when employedwith other binders will also act as a crosslinking agent to produce ahighly-crosslinked coating upon curing or drying of the film.Accordingly, it may be part of or all of the needed crosslinking agentand binder in the paint system.

Accordingly, the compositions and materials of this invention can beused alone or in conjunction with other resins as polymeric coatings onsurface. These coatings will crosslink or self-crosslink and can be usedin conjunction with other crosslinking agents such as melamineformaldehyde or urea-formaldehyde resins as well as phenolic resins,epxoy resins, isocyanates and blocked isocyanates. The Mannich adductscan also be used to crosslink with vinyl functionality as is present inresins such as diallylmelamine, butadiene, multifunctional acrylicoligomers, unsaturated fatty acids in alkyd resins, fatty acid modifiedepoxy resins, and the like.

Application of the treatment compositions of the present invention inthe treatment step to a metal or other desired surface can be carriedout by any conventional method. (While it is contemplated that the metalsurface will preferably be a conversion coated metal surface, thetreatment step can alternatively be carried out on an otherwiseuntreated metal surface to improve the corrosion resistance and paintadhesion thereof.)

For example, the treatment composition can be applied by spray coating,roller coating, or dipping. The temperature of the solution applied canvary over a wide range, but is preferably from 70° F. to 160° F. Afterapplication of the treatment solution to the metal surface, the surfacecan optionally be rinsed, although good results can be obtained withoutrinsing after treatment. Rinsing may be preferred for some end uses, forexample, in electrocoat paint application.

Optionally, the treated metal surface is dried. Drying can be carriedout by, for example, circulating air or oven drying. While roomtemperature drying can be employed, the use of elevated temperatures ispreferred to decrease the amount of drying time required.

After drying (if desired) the treated metal surface is then ready forpainting (with or without the Polymer Materials of the presentinvention) or the like. Suitable standard paint or other coatingapplication techniques such as brush painting, spray painting,electro-static coating, dipping, roller coating, as well aselectrocoating, may be employed. As a result of the treatment step ofthe present invention, the conversion coated surface has improved paintadhesion and corrosion resistance characteristics.

Further understanding of the present invention can be had from thefollowing illustrative examples. As used herein "salt spray" refers tosalt spray corrosion resistance measured in accordance withASTM-B117-61. As used herein, "Scotch Tape Adhesion" refers to the 180°T-bend adhesion test as described in ASTM-D3794-79. In summary, panelsare scribed in the center and subjected to the ASTM tests. The ratingtests for corrosion are measurements of the amount of "creeping" thepaint does from the scribe in units of 1/16 of an inch. The superscriptsrepresent the number of spots that are present.

EXAMPLE 1

80 g of a resin having an average molecular weight average of about 2400and wherein R₁, R₁₃, R₁₄ and W₂ are H, R₂ is --CH₃ and Y₂ is Z (based onFormula I herein) is slowly dissolved in 160 mls of Propasol P (apropoxylated propanol solvent obtained from Union Carbide Corp.,Danbury, Conn.) in a 1 liter resin flask, using a high speed mixer. Theresin flask is fitted with a blade stirrer, reflux condenser, andnitrogen purge. The resin solution is then charged with 53.5 mls of2-(methylamino)-ethanol and 160 mls deionized water. Gentle heating to60° C. is started. When 60° C. is reached, addition of 50 mls of 37%formaldehyde is begun and continued over a one hour period. Anadditional 25 mls Propasol P is added and the mixture maintained at 60°C. for 1.5 hours. The temperature is raised to 80° C. and held for 1.75hours. The reaction mixture is allowed to cool to room temperature and21.8 g of 75% H₃ PO₄ followed by 960 mls deionized water is added.Optionally, an amine oxide is formed that does not require theadditional neutralization step by adding 0.75 mole of 30% H₂ O₂ (85 g)to the reaction mixture. The reaction is allowed to stir overnight, andis then diluted with 960 ml of deionized water. The result of thisoptional step is a water soluble amine oxide resin that does not requireneutralization for water stability.

Dilute solutions of the above formulation were applied to phosphatedmetal at 120° F. for various times by spray application. In a typicalmetal treatment operation, the metal to be treated is initially cleanedby a mineral spirits wipe, followed by PARCO® CLEANER 338 (ParkerChemical Company) for 60 seconds at 160° F., followed by a hot waterrinse for 30 seconds, 60 seconds BONDERITE® 1000 (Parker ChemicalCompany) treatment at 155° F., 30 seconds cold water rinse, and then thepost treatment. Some of the panels were rinsed after post-treatment,others were not rinsed. All panels were then baked in a 350° F. oven for5 minutes.

The treated panels were painted with Duracron 200 (PPG Industries,Pittsburgh, Penn.) paint. The paint was scribed, and the panelssubjected to salt spray accelerated testing for 504 hours and comparedto Parcolene 95 and PARCOLENE® 60 controls. Test results for severalvariations are provided in Table I. (®--PARCO, BONDERITE and PARCOLENEare registered trademarks of the Parker Chemical Company)

EXAMPLE 2

Reaction of a higher molecular weight version of the resin used inExample 1, (M_(w) 3800, M_(n) 1300) with 2-(methylamino) ethanol ("MEA")and formaldehyde following the same cook as for the resin in Example 1.

                  TABLE I                                                         ______________________________________                                        ACCELERATED AND PHYSICAL TESTS                                                                        504 Hrs.  Scotch Tape                                 Post-Treatment                                                                           Concentration/pH                                                                           Salt Spray                                                                              Adhesion                                    ______________________________________                                        Parcolene 60                                                                             --/4.5       N         10                                          Control                                                                       Deionized Water         6-8       10                                          Resin of Ex. 1                                                                           .1%/pH 6.1     0-1.sup.2s                                                                            --                                          derivative                                                                    Resin of Ex. 1                                                                           .1%/pH 4.0     0-1.sup.1s                                                                            --                                          derivative                                                                    Resin of Ex. 2                                                                           .1%/pH 6.1   1-2       10                                          derivative                                                                    Resin of Ex. 2                                                                           .1%/pH 3.8   0-1       10                                          derivative                                                                    ______________________________________                                    

EXAMPLE 3

Reaction of vinyl phenol methyl methacrylate co-polymer withmethylethanolamine and formaldehyde.

80 g of a poly-4-vinylphenol methyl methacrylate co-polymer (fromMaruzen Oil Co. of U.S.A., Inc., New York, N.Y. M_(w) 14,090 and M_(n)6,800, PVP/MMA 57/43 weight ratio) was dissolved in 160 mls Proposal P.29.2 mls (0.36 equivs) of 99% methylethanolamine is added, followed by160 mls deionized water. The mixture was brought to 45°-50° C., then27.3 mls (0.36 equivs) of 37% aqueous formaldehyde was added dropwiseover one hour while maintaining the reaction mixture at 45°-50° C. Thereaction mixture was then warmed to 80° C. and maintained at thistemperature for four (4) hours. After cooling to ambient temperature, 24g of 75% phosphoric acid and 536 mls deionized water added in portionswith good stirring. The resulting solution had a pH of 6.6, and solidscontent of 13.7%.

The above product was used as a post-treatment for Bonderite 1000 overcold rolled steel 4"×12" test panels in concentrations of 0.05%, 0.1%and 0.90% solids and pH's of 6.1-6.2 and 4.0. Application was via spraytank for 15, 30 and 60 seconds. Partial results are listed below for theDuracron 200 paint system.

    ______________________________________                                                                  504 Hrs.                                            Post-Teatment     Time    Salt Spray                                          ______________________________________                                        Resin of Example 3                                                                              15 sec  1-2                                                 Resin of Example 3                                                                              60 sec  1-1                                                 Parcolene 60      30 sec  N                                                   None              N/A     2-4                                                 ______________________________________                                    

EXAMPLE 4

Reaction of a polyvinyl phenol novolak co-polymer withmethylethanolamine and formaldehyde (M_(w) 4,200, M_(n) 1,330).

80 g of the resin was dissolved in 160 mls Proposal P. 53.5 mls (0.66equivs) methylethanolamine and 160 mls deionized water was added and thetemperature brought to 45°-50° C. Next, 50 mls (0.66 equivs) 37%formaldehyde was added dropwise over one hour. The temperature wasmaintained between 45° and 50° C. for an additional two (2) hours,heated to 80° C., and maintained at 80° C. for two (2) hours. Aftercooling to ambient temperature, 21.7 g of 75% phosphoric acid and 993mls of deionized water was added.

EXAMPLE 5

A polyvinyl phenol-cresol novolak co-polymer (M_(w) 6,050, M_(n) 1,600)was reacted in the same proportions with MEA and CH₂ O as in Example 4,but had to cook for six (6) hours at 80°-90° C. to reduce formaldehydeconcentration to 0.6%. For water solubility, (in 993 mls deionizedwater), enough 75% phosphoric acid was added to bring pH of reactionproduct to 3.7. Solids 12.2%.

EXAMPLE 6

A polyvinyl phenol ("PVP") novolak co-polymer (M_(w) 3,190, M_(n) 1,120)was reacted in the same manner as in Example 4, except 46 g of 75%phosphoric acid was required to solubilize the product in water (finalpH=4.9).

EXAMPLE 7

A PVP-novolak co-polymer (M_(w) 3,460, M_(n) 1,170) was reacted in thesame manner as in Example 4, except 61 g of 75% phosphoric acid wasneeded to solubilize the product in water (final pH=5.0).

    ______________________________________                                        Post-Treatment    Time    pH    Salt Spray                                    ______________________________________                                        0.1% Example 4 derivative                                                                       30      4.1    0-1.sup.s                                    0.1% Example 4 derivative                                                                       30      6.3   N                                             PARCOLENE 60      30      4.0   N                                             None              --      --    7-8                                           0.1% Example 6 derivative                                                                       30      6.0     0-1.sup.2s                                  0.1% Example 6 derivative                                                                       60      6.0     0-1.sup.6s                                  0.1% Example 6 derivative                                                                       30      4     1-3                                           PARCOLENE 60      30      4.0   N                                             None              --      --    4-6                                           0.1% Example 7 derivative                                                                       30      6.0    0-1.sup.s                                    0.1% Example 7 derivative                                                                       60      6.0    0-1.sup.s                                    0.1% Example 7 derivative                                                                       30      4.1    0-1.sup.s                                    PARCOLENE 60      30      4.0    0-1.sup.s                                    None              --      --    4-6                                           0.05% Example 5 derivative                                                                      30      6.2   0-1                                           0.1% Example 5 derivative                                                                       30      6.3     1-2.sup.3s                                  0.1% Example 5 derivative                                                                       60      6.3     0-2                                         0.1% Example 5 derivative                                                                       30      4.0   0-1.sup.2s                                    PARCOLENE 60      30      4.5   N                                             None              --      --      5-6.sup.9s                                  ______________________________________                                    

EXAMPLE 8

Reaction of a polyvinylphenol resin in which 20% of the phenolichydrogens have been replaced by 2-hydroxypropyl-1,3,5-trimethylhexanoate with methylethanolamine andformaldehyde.

83 g of the resin was dissolved in 271 g Propasol P, 30 g (0.40 equivs)methylethanolamine was added and the mixture warmed to 60° C. Next, 30mls (0.40 equivs) of 37% formaldehyde was added over one hour. Thetemperature was held at 60° C. for an additional hour, then heated to80° C. for four (4) hours. A formaldehyde titration at this time of thereaction mixture yielded 0.93% formaldehyde. The mixture was warmed to90° C. and held at 90° C. for six (6) hours. Formaldehyde concentrationhad dropped to 0.4% by titration. After cooling to ambient temperature,13 g of 75% phosphoric acid and 600 mls deionized water was added withgood stirring. The resulting solution had a pH of 6.8 and solids contentof 9.5%.

EXAMPLE 9

A polyvinylphenol resin in which 30% of the phenolic hydrogens have beenreplaced by 2-hydroxy propyl-1,3,5-trimethylhexanote was reacted withmethylethanolamine and formaldehyde in the same manner as in Example 8,except the ratios of ingredients was changed. Propasol P--300 mls;Resin--94.2 g; 99% methylethanolamine--28.4 mls (0.35 mols); 37%formaldehyde--26.3 mls (0.35 mols). The formaldehyde was added over onehour while maintaining the temperature at 60° C.; the reaction mixturewas maintained at 60° C. for an additional hour, heated to 90° C. andmaintained for an additional four (4) hours. After cooling, enough 75%phosphoric acid to bring the pH to 5.0 and 600 mls deionized water wasadded. Solids on the final product was 13.5%.

The above product was used as a post-treatment for BONDERITE 1000 over4"×12" cold rolled steel panels as described previously. Some testresults are listed below:

    ______________________________________                                                                  504 Hrs.                                            Post-Treatment     Time   Salt Spray                                          ______________________________________                                        Example 8 derivative                                                                             15 s     0-1.sup.2s                                        Example 8 derivative                                                                             60 s     0-1.sup.2s                                        PARCOLENE 60       30 s   N                                                   None               --     6-7                                                 Example 9 derivative                                                                             15 s    0-1.sup.s                                          Example 9 derivative                                                                             60 s   0-1                                                 PARCOLENE 60       30 s   0-1                                                 None               --      7-11                                               ______________________________________                                    

EXAMPLE 10

Into a one (1) liter reactor equipped with a reflux condensor, nitrogensparge, thermocouple and addition funnel was added 450 ml of butylcellosolve (Union Carbide). To the solvent over a 90 minute period wasslowly added 180 grams of poly-4-vinylphenol powder (M.W._(w) =5,000)with good agitation. The temperature was then increased to 100° C. todissolve any resin from the walls of the flask and then 89.25 grams ofAraldite DY 025, (Ciba Geigy) a mono-functional epoxide was addedfollowed by the addition of one (1) gram of N,N-Dimethylbenzylamine. Thetemperature was gradually increased and the reaction mildly exothermedto 167° C. The reaction was post-heated at 175°-185° C. for anadditional 3 hours and then cooled. (The final solids of the reactionwas 40.3% (baked at 350° F. for 15 minutes) indicating a 99% completionof the reaction.)

The epoxide modified poly-4-vinylphenol derivative from above was usedin the preparation of a Mannich derivative as outlined below. 90.13grams of 2-(N-methylamino)-ethanol was added to the reaction product andsolvent above, and the mixture was heated to 50° C. Over a 45 minuteperiod 97.4 grams of a 37% formaldehyde solution was then added and thenthe reaction was post-heated for the first 2 hours at 50° C. and then 3hours at 80° C. (The reaction was found to be complete by titration forresidual formaldehyde.)

A portion of the above solution was adjusted to a pH of 6.5 withphosphoric acid and diluted to 17% solids with deionized water. Zincphosphated cold rolled steel panels (Bonderite® EP-1) were dipped intothe diluted solution of the above polymer and was electrolyticallyapplied to the cold rolled steel panel using a DC current where thepanel was made the cathode and a 316 stainless steel panel was made theanode. The cold rolled steel panels were withdrawn from the treatmentbath, rinsed with deionized water and oven baked at 400° F. for 20minutes. A coating thickness of approximately 0.5 mls was attained. Thecoating is tested by treatment with methyl ethyl ketone (MEK) andsimultaneously rubbed with a cloth, good solvent resistance is obtained.

The above polymer solution in water was also cast on a zinc phosphatedcold rolled steel panel (Bonderite® EP-1) by the use of a draw-down barand then baked at 400° F./20 minutes. Again, good MEK resistance resultsafter the oven-bake, while without an oven curing step less thanfavorable MEK test results are obtained. These results indicate that theMannich derivative of the polymer above is self-crosslinking and can beused to form a coating on a metal surface by either casting a film or bycathodic electrodeposition. Good solvent resistance can be obtainedwithout the addition of external crosslinking agents, althoughsubstantially similar results may be obtained by adding externalcrosslinking agents. Such materials may accordingly be applied eitherelectrolytically or non-electrolytically.

EXAMPLE 11

A Mannich adduct of poly-4-vinylphenol with N,N-diallylamine wasprepared as above by reacting the following ingredients.

1. 131.2 grams 30.5% poly-4-vinylphenol in Propasol P (supplied by UnionCarbide)

2. 27.5 grams of Propasol P

3. 33.4 grams of N,N-diallylamine (supplied by Aldrich Chemical Co)

4. 26.4 grams of a 37.9% formaldehyde solution.

The ingredients were mixed and reacted for approximately five hours at50° C. and then for 2 hours at 80° C. This reaction was characterized bythe consumption disappearance of formaldehyde and the reaction stoppedwhen approximately 99% complete.

The reaction mixture of poly-4-vinylphenol, N,N-diallylamine andformaldehyde from above was diluted to 17.5% solids with solvent(Propasol P) and applied to a cleaned aluminum panel (#3003 alloy) by aconventional non electrolytic method such as spraying. A wet filmthickness of 3 mils was obtained; a dry film thickness of approximately1 mil was attained after baking at 350° C. for ten minutes. MEK (methylethyl ketone) solvent resistance of 500+ double rubs was obtained.

The above N,N-diallylamine Mannich adduct of poly-4-vinylphenol producedabove in Example 11 was mixed in approximately 10 parts by weightMannich to 12 parts by weight Monsanto RJ-101 resin (a stryene-allylalcohol copolymer supplied by Monsanto). This polymeric coatingformulation was applied to an aluminum panel using a draw down bar andbaked in a convection oven at 350° F. for 10 minutes. No failure of thecured coating was noted after 500+ MEK double rubs.

A coating applied by a convention non-electrolytic method omitting theadduct (employing only the Monsanto RJ-101 Polymer) failed inapproximately 10 MEK double rubs. The above results indicate that thecompositions of the present invention, whether used alone or incombination with other agents, (i.e. Mannich derivatives ofpolyvinylphenols) are excellent crosslinking agents for polymericsystems or can be used as polymeric coatings possessingself-crosslinking properties.

What is claimed is:
 1. A composition comprising a surface treatmentcarrier having dissolved or dispersed therein a polymer compoundcomprising a polymer material having at least one unit having theformula: ##STR5## wherein: R₁, R₂, R₁₃ and R₁₄ are independentlyselected for each of said units from hydrogen, an alkyl group havingfrom 1 to about 5 carbon atoms or aryl group having from about 6 toabout 18 carbon atoms;Y₂ is independently selected for each of suchunits from hydrogen, Z, --CR₁₁ R₅ OR₆, --CH₂ Cl, or an alkyl or arylgroup having from 1 to 18 carbon atoms provided that at least a fractionof one Y₂ in one of said units is Z; Z is ##STR6## wherein R₅ throughR₁₂ are independently selected for each of such units from hydrogen, oran alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl orphospho-alkyl moiety; R₁₂ may also be selected from --O.sup.(-1) or--OH; and W₂ is independently selected for each repeating unit from thegroup consisting of hydrogen; an acyl moiety; acetyl; benzoyl moiety;3-allyloxy-2-hydroxypropyl; 3-benzyloxy-2-hydroxy-propyl;3-alkylbenzyloxy-2-hydroxy-propyl; 3-phenoxy-2-hydroxy-propyl;3-alkylphenoxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl;3-alkyloxy-2-hydroxy-propyl; 2-hydroxyoctyl; 2-hydroxy-alkyl;2-hydroxy-2-phenyl ethyl; 2-hydroxy-2-alkylphenyl ethyl; benzyl; ethyl;methyl; propyl; alkyl; allyl; alkylbenzyl; haloalkyl; haloalkenyl;2-chloropropenyl; sodium, potassium; tetra aryl ammonium; tetra alkylammonium; tetra alkyl phosphonium; tetra aryl phosphonium; or acondensation product of ethylene oxide, propylene oxide, or mixturesthereof.
 2. A composition according to claim 1 wherein the carriercomprises water.
 3. A composition according to claim 1 wherein thecarrier is aqueous and the polymer has been neutralized with an acid. 4.A composition according to claim 3 wherein the acid is carbonic acid. 5.A composition according to claim 3 having a pH of from about 0.5 toabout
 14. 6. A composition according to claim 3 having a pH of fromabout 2.0 to about
 12. 7. A composition according to claim 1 whereinsaid polymer compound comprises about 0.001 to about 80% by weight ofthe final composition.
 8. A composition according to claim 7 whereinsaid polymer compound comprises from about 0.001% to about 10% of saidcomposition.
 9. A composition according to claim 8 wherein said polymercompound comprises from about 0.001 to about 5% of said composition. 10.A composition according to claim 9 wherein said polymer compoundcomprises from about 0.025% to about 1% of said composition.
 11. Acomposition according to claim 7 wherein said polymer compound comprisesfrom about 1% to about 80% of said composition.
 12. A compositionaccording to claim 5 which additionally comprises a complex fluoridematerial.
 13. A composition according to claim 1 which additionallycomprises a dissolved or dispersed compound that includes compounds oftitanium, zirconium, hafnium, silicon, or mixtures thereof.
 14. Acomposition according to claim 1 which additionally comprises an oxideof silicon, titanium, tin, aluminum, cobalt, nickel, or mixturesthereof.
 15. A composition according to claim 1 which additionallycomprises a paint system additive selected from the group consisting ofa film forming resin, a pigment, a binder, particulate zinc, or mixturesthereof.
 16. A composition formed by condensing:a polymer compoundcomprising a polymer material having at least one unit having theformula: ##STR7## wherein: R₁, R₂, R₁₃ and R₁₄ are independentlyselected for each of said units from hydrogen, an alkyl group havingfrom 1 to about 5 carbon atoms or aryl group having from about 6 toabout 18 carbon atoms; Y₂ is independently selected for each of suchunits from hydrogen, Z, --CR₁₁ R₅ OR₆, --CH₂ Cl, or an alkyl or arylgroup having from 1 to 18 carbon atoms provided that at least a fractionof one Y₂ in one of said units is Z; Z is ##STR8## wherein R₅ throughR₁₂ are independently selected for each of such units from hydrogen, oran alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl orphospho-alkyl moiety; R₁₂ may also be selected from --O.sup.(-1) or--OH; and W₂ is independently selected for each repeating unit from thegroup consisting of hydrogen; an acyl moiety; acetyl; benzoyl moiety;3-allyloxy-2-hydroxypropyl; 3-benzyloxy-2-hydroxy-propyl;3-alkylbenzyloxy-2-hydroxy-propyl; 3-phenoxy-2-hydroxy-propyl;3-alkylphenoxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl;3-alkyloxy-2-hydroxy-propyl; 2-hydroxyoctyl; 2-hydroxy-alkyl;2-hydroxy-2-phenyl ethyl; 2-hydroxy-2-alkylphenyl ethyl; benzyl; ethyl;methyl; propyl; alkyl; allyl; alkylbenzyl; haloalkyl; haloalkenyl;2-chloropropenyl; sodium, potassium; tetra aryl ammonium; tetra alkylammonium; tetra alkyl phosphonium; tetra aryl phosphonium; or acondensation product of ethylene oxide, propylene oxide, or mixturesthereofwith a second compound selected from the group consisting ofphenols, tannins, novolak resins, lignin compounds, together withaldehydes, ketones or mixtures thereof, to produce a condensation resinproduct, said condensation resin product then being further reacted bythe addition of "Z" to at least a portion of it by reacting said resinproduct with (1) an aldehyde or ketone and (2) a secondary amineproducing a final adduct which can react with an acid.
 17. A compositionaccording to claim 16 wherein the second compound is a phenol and isselected from the group consisting of phenol, alkylphenol, arylphenol,cresol, resorcinol, catechol, pyrogallol, and mixtures thereof.